The polymerization of diphenol polyhedral oligomeric silsequioxane (2OH-DDSQ) with a series of perfluoro-monomers including decafluorobiphenyl, decaflurobenzophenone and decafluorodiphenyl sulfone was studied to obtain the optimized reaction for the preparation of POSS-containing fluorinated poly(arylene ether)s. The kinetic behavior of the polymerizations was studied. All the reactants show high reactivity even at a low temperature (30 °C in DMAc). Results show that the polymerization rate increases with the increasing polarity of the perfluoro-monomers and the polymerization of 2OH-DDSQ with decafluorodiphenyl sulfone exhibits the highest rate constant at low temperatures of 30 °C, 40 °C and 45 °C. All of the reaction systems were slightly influenced by the reaction temperature due to the low activation energy. The thermal properties of the polymers were also studied.